Halogenated siloxanes



2,884,433 moon arn a snoxANEs This invention relates to siloxanes derived from divinyl silanes having a halogenated cyclobutyl group, a triisohexyl group on the silicon, I v More specifically this in ention relates to a compound of the unit formula. I

where R is selected from? the group consisting of aryl, alkyl and cyclo alkyl hydrocarbon radicals and X is selected fromthe group consisting of CF CH CI I C F: ,QFsCHrCHrCIiCH the formula CJ-I F CL- and R can be any alkyl hydrocarbon radical, e.g. methyl, Z-ethyl-hexyl and octadecyl; any cycloalkylhydrocarbon a cyclobutyl group of radicals, e.g. cyclopentyl and 'cyclohexyl; and any aryl q hydrocarbon radical, e.g. 'phenyl, tolyl,

xenyl and naph- X be CFSCHZCHQE,

C F 3 C F CH CHzCHCHrortho-, meta-, and para-trifiuorotolyl radicals,

crow membnand Error (nomin- The chlorotrifluorocyclobutyl radicals are best attached to silicon as shown in the copending application of Arthur Gordon, Serial 1No .-494,287, filed March 14, 1955.

The radicals CF 'CH CH and f-..crea si ware bestattachednto silicon by reacting-the corresponding olefins with SiH compounds at elevated temperatures.

The silylethylsiloxanes .of this invention can be prepared by reacting silanes of the formula F a R ,4 ylslx where X and R are as above defined and Y is a hydrolyzable group such .as halogen,v e.g. chlorine, bromine, and iodine, or an alkoxy radical, e.g. methoxy and butoxy, with vinyl Grignardi to-form-a divinyl silane. A preferred method for the preparation of vinyl Grignard reagents is disclosed by H.3Normant, ,Compt. rend. 239, 1510, 1811; ibid., 240, 31-4, 440, 631.:

Subsequently, the vinylsilane is reacted with a symmetrical tetraorganodisiloxane where the organic radicals are defined by R above. This reaction is best accom- 'plished by cautiously heating the vinylsilane to 100C. (or its boilingpoint if less than 100 C.) with a catalyst suchas platinum on charcoal or chloroplatinic acid in dimethylcarbitoluntil'the reaction becomes spontaneous silylethylpolysiloxane where R and Y'are as with a silane of the formula Pa ent Apr, 28,1959

and'ma'intaining the reaction temperature between 150-- The preferred method of preparation is that of employingthe above Grignard'rea'ction to form a divinyl silane x IQHFCH%CH =CHI which is reacted with a diorganomonohalosilane Ra HSiY to form the disilylethyldihalosilcarhane which can be hydrolyzed and condensed to form" the An alternative of this method is the production a: a

silane of the formula l R:- CH1=CHS1Y A above defined, subsequent reaction where X and R are as above defined and hydrolysis and condensation of the disilylethylsilcarbane to the polysiloxane. If desired the R2 OHFCHSiY silanes may first be condensed to disiloxanes and then reacted with radicals above defined, to prevent extraneous and deleterious side reactions.

The siloxanes of this invention can be copolymerized to form copolymers comprising from 0.1 to 99.9 mol percent of the siloxanes of this invention and from 99.9

, to 0.1 molpercent of compositions of the unit formula value of from 1 to 3 inclusive. These copolymers can be prepared by any means of copolymerization such as cohydrolyzing a mixture of haloor alkoxy-silanes of the formulae and Z,,,SiY., where X, R, Z, Y, and m are as above defined and condensing the polysiloxane copolymer. Another method of preparation of the copolymers'of this invention is catalytic copolymerization of the siloxanes of this invention with siloxanes of the formula preferably in the presence of an acid catalyst.

erties: B.P. C.), 89/30 mm.; r2 1.3903. quent reaction of the divinylsilane with sym-tetramethyl- Z can therefore be alkyl, e.g. methyl, Z-ethylhexyl and octadecyl; cycloalkyl, e.g. cyclohexyl and cyclopentyl; halogenated alkyl, e.g. 2,3-dibromopropyl and 4-trifluoro methyldecyl; halogenated cycloalkyl, e.g. 2,4,6-triiodocyclohexyl; aryl, e.g. phenyl, xenyl and naphthyl; halogenated aryl, e.g. 2,4-dichlorophenyl, B-bromonaphthyl, and bromoxenyl; aralkyl, e.g. benzyl; halogenated aralkyl, e.g. a-chlorobenzyl and 2,4-dichlorobenzyl; alkaryl, e.g. tolyl; halogenated alkaryl, e.g. trifluorotolyl; alkenyl, e.g. vinyl, allyl and 5,6-octadecenyl; cycloalkenyl, e.g. 2,3- cyclopentenyl; halogenated alkenyl, e.g. 3-iodoallyl, symdibromovinyl; and halogenated cycloalkenyl, e.g. 4,5- dichloro-2,3-cyclohexenyl. Z can also be any of the groups defined by X.

The siloxanes of this invention are especially useful as lubricants. They are also useful as coatings, elastomers, and molding resins.

The following examples are illustrative only and should not be construed as limiting the invention which is properly set forth in the appended claims.

in an equal volume of tetrahydrofuran, and the solution was added slowly with stirring to a solution of vinyl Grignard in tetrahydrofuran in a ratio of one mol of silane to two mols of Grignard reagent. During the reaction the reaction flask was cooled by an ice water bath. When the silane addition was complete, the reaction mixture was allowed to warm to room temperature. The contents of the reaction flask were poured into an ice water mixture, and hydrochloric acid was added to dissolve magnesium salts. The organic layer was separated, washed with water several times to remove most of the tetrahydrofuran, and dried with calcium hydride. dried organic layer was distilled and a 52% yield of trifluoropropylmethyldivinylsilane was obtained with the following properties: B.P. C.), 134/atm.; 11 1.395.

(b) This silane was heated to 100 C. with a catalyst composed of .06% by weight platinum on charcoal. The catalyst was employed in amount so that there was one gram of catalyst per mol of silane. Sym-tetramethyldisiloxane was added slowly so that the temperature of the spontaneous reaction was maintained in the range 150- 175 C. until the addition was complete. The reaction mixture was cooled, diluted with ether and filtered. The ether was removed by distillation at atmospheric pressure. The residual fluid was heated to 150 C. at a pressure of approximately 1 mm. Hg to remove low molecular weight materials and was refiltered. The product was a fluid polymer of the unit formula with various loads. The results (scar diameter in millimeter's) were as follows:

Lnad

40 Sea Example 2 ,5 ,S-trifluoro-Z (trifluoromethyl) amylmethyldiehlorosilane was substituted for the silane of Example 1(a). A 56% yield of 5,5,5 trifiuoro 2 (trifluoromethyl)amylmethyldivinylsilane was obtained with the following prop- Subsedisiloxane according to the method of Example 1 produced a polymer of the unit formula The This polymer was tested for lubricity according to the method of Example 1. The results were as follows:

Example 3 FClGFlCHs and HSKCH=CH|B and polymers of the unit formulae respectively. The siloxanes were suitable as lubricants.

Example 4 When monochlor'odimethyls'ilane was substituted for the sym-tetramethyldisilox'anc of Example 1(b) and the resulting product was hydrolyzed, a fluid polysiloxane of the unit formula s ii'cm i cm) ill 'icl gm 1 I was obtained.

Example 5 When methyl 3,3,3 trifluoropropyldivinylsilane and phenyloctadecylmonochlorosilanc are reacted in accordance with the method of Example 1 in a molar ratio of 1:2 and the reaction product is hydrolyzed and condensed with diehlorophenylvinyldichlorosilane in a molar ratio of one mol of the reaction product to one mol of the dichlorosilane, a. thermoplastic copolymer istormed con- When p e,e,a trifluorotolyl-2-ethyl-hexyldivinylsllane and dixenylmonoethoxysilane are reacted in accordance with the method of Example 1 in a molar ratio of 1:2 and the reaction product is cohydrolyzed and eocondensed with bis-3,3,3-trifluoropropyldiethoxysilane "in a rnolar ratio of two mols of the reaction product to one mol of the diethoxysilane, the resulting thermoplastic copolymer consists of [159 10310 Rho 1 units.

Example 7 When 5,5,5-trifluoro-2-trifluoromethylamyltolyldivinylsilane and dicyclohexylmonochlorosilane are reacted in accordance with the method 'of Example 1 in a molar ratio of 1:2 and the reaction product is cohydrolyzcdand cocondensed with tolyl-3,4-cyclopentenyl-Z-ethyl-hexylchlorosilance in a molar ratio of 1:1, there results a fluid copolymer which consists of orlomonmort 1 When 3,3,3 trifluoropropylphenyldivinylsilane and methylnaphthyl monochlorosilane are reacted in accordance with the method of Example 1 in a molar ratio of 1:2 and the reaction product is hydrolyzed and condensed with silicon tetrachloride in a molar ratio of four mols of the reaction product to one mol of silicon tetrachloride, a resinous copolymer results which consists of and [SiO units.

Example 9 When 3,7,7 trifluoro-fi-chlorocyclobutylphenyldivinylsilane and dimethylmonochlorosilane are reacted in accordance with the method of Example 1 in a molar ratio of 1:2 and the reaction product is hydrolyzed and condensed with benzyltrichlorosilane in a molar ratio of five 6 mols of the reaction product per mol of the trichlorosilane, a resinous copolymer results which consists of Me: Ph Men [Sl(CH|)2Sl(CH:)P-SlO-] crow From and @1 1.0 umts.

Example 10 When an equimolar mixture of trifluorotolylmethyl divinylsilane, 5, trifluoro fl-chlorocyclobutylphenyldivinylsilane, phenylbutylmonochlorosilane and 2-ethylhexylxenylmonochlorosilane is reacted in accordance with the method of Example 1 and the reaction product is hydrolyzed and condensed with an equimolar mixture of cyclohexyltrichlorosilane, phenyl-Z-ethyl-6-bromo-hexylamylchlorosilane, tolylbenzyldichlorosilane and silicon tetrachloride, a copolymer results which consists of;1 2. 5 mol percent each of the following units:

Me(OH)CHEt on 0H H Ph [S102], [@SiOm] CH: Ph and I: CHrCH-(CHzhCHaBlJ rhM That which is claimed is: 1. A compoundof the unit formula where R is selected from the group consisting of aryl, alkyl and cycloalkyl hydrocarbon radicals and X is selected from the group consisting of V or GFiCHaCHr-, cmomcmorr'omand 2. A compound of the unit formula 8 3. A compound of the unit formula Me; Me Me: [-S1(CH:)aSl(CH:)a-Sl0] omorrornonior, 4. A compound of the unit formula Me: Me Me:

Si(CH:)rSi(CHr):-Si0

CH2 H FY- FY where one Y is fluorine and the other Y is chlorine.

5. A compound of the unit formula Me: Me Me: Bi(CH:):Si(CHz) P810- 6. A copolymer comprising from 0.1 to 99.9 percent of (1) a composition of the unit formula where R is selected from the group consisting of aryl, alkyl and cycloalkyl hydrocarbon radicals and X is selected from the group consisting of or omcmor-n cmomomcncrnvalent hydrocarbon radicals and their halogenated derivatives and m has an average value from 1 to inclusive.

References Cited in the file of this patent FOREIGN PATENTS 1,116,316 France Ian. 30, 1956 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,884,433 April 28, 1959 Donald D. Smith It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, lines 30 to 37 inclusive, Example 7, first formula should appear as shown below instead of as in the patent- K51 QM same column 5, lines 58 to 66 inclusive, Example 8, the formula should appear as shown below instead of as in the patent- CHaC Fa column 7 lines 20 and 21, claim 1, the formula should appear as shown below instead of as in the patent- C FsCH2CHg-, C FaCHzCHaOH CHr, F10 FCICH: H, FClC FaCHgCH- Signed and sealed this 8th day of September 1959.

[SEAL] Attest I KARL AXLINE, i ROBERT C. WATSON,

Attest'ing Oflice'r. v (Jowwm'ssz'oner of Patents. 

1. A COMPOUND OF THE UNIT FORMULA 